In this paper, we study the effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La（1-x）PrxFe11.4Si1.6Hy hydrides. The powder x-ray diffraction patterns of the La1-xPrxFe11.4Si1.6...In this paper, we study the effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La（1-x）PrxFe11.4Si1.6Hy hydrides. The powder x-ray diffraction patterns of the La1-xPrxFe11.4Si1.6 and its hydrides show that each of the alloys is crystallized into the single phase of cubic Na Zn13-type structure. There are hydrogen-absorbing plateaus under 0.4938 MPa and 0.4882 MPa in the absorbing curves for the La0.8Pr0.2Fe11.4Si1.6 and La0.6Pr0.4Fe11.4Si1.6 compounds. The releasing processes lag behind the absorbing process, which is obviously different from the coincidence between absorbing and releasing curves of the La Fe11.4Si1.6 compound. The remnant hydrogen content for La0.6Pr0.4Fe11.4Si1.6 is significantly more than that for La0.8Pr0.2Fe11.4Si1.6 after hydrogen desorption, indicating that more substitutions of Pr for La are beneficial to retaining more hydrogen atoms in the alloys. The values of maximum magnetic entropy change are 14.91 J/kg·K and 17.995 J/kg·K for La0.8Pr0.2Fe11.4Si1.6H0.13 and La0.6Pr0.4Fe11.4Si1.6H0.87,respectively.展开更多
NizP supported catalysts exhibit high catalytic activities in hydrogenation reaction,of which the particle sizes of Ni_(2)P active phases are the key influential factor.This research focus on the effect of chelators o...NizP supported catalysts exhibit high catalytic activities in hydrogenation reaction,of which the particle sizes of Ni_(2)P active phases are the key influential factor.This research focus on the effect of chelators on the size of Ni_(2)P particles over wrinkle silica nanoparticles(WSNs)by introducing chelating agents EDTA and NTA during impregnation process.The characterization results show that chelators modified cata-lysts possess smaller size of Ni_(2)P particles than the unmodified Ni_(2)P catalysts.Among all the synthesized catalysts,the EDTA modified Ni_(2)PE(1.5)/WSNs catalyst possesses smallest average particle size of Ni_(2)P,only 2.6 nm.Moreover,the Ni_(2)P catalysts with the assistance of EDTA exhibits better catalytic activity than that of NTA under high reaction temperature,which can be ascribed to the strong bonding between EDTA and Ni.And the EDTA modified Ni_(2)PE(1.5)/WSNs catalyst shows highest hydrogenation ability,almost reaching 100%decalin selectivity.展开更多
The phenomenon of hydrogen thermoemission out of a crystal lattice of powder rare-earth metals trihydrooxides R(OH)3 (R is La, Pr, Nd) was found. The hydrogen thermoemission out of a crystal lattice is partial or full...The phenomenon of hydrogen thermoemission out of a crystal lattice of powder rare-earth metals trihydrooxides R(OH)3 (R is La, Pr, Nd) was found. The hydrogen thermoemission out of a crystal lattice is partial or full removal of hydrogen out of the crystal lattice of powder hydrogen-containing crystal without change of symmetry of such crystal at continuous evacuation of high vacuum at evacuation temperature of Тev. which is lower than recrystallization Тrecrys. or disintegration (Tdisinteg.) temperature of this crystal: Тev. Тrecrys. Tdisineg.. By neutron diffraction it is found that low- temperature (Тevacuation = 400 - 420 K ) removal of hydrogen (by hydrogen thermoemission) out of a crystal lattice of trihydrooxide R(OH)3 under continuous high vacuum evacuating makes possible to obtain metastable “trioxide” R[O]3. Existence of such substance contradicts to the valence law (oxygen is bivalent and Pr is trivalent in hydroxides). Such “trioxide” has a superfluous negative charge: R3+O6-. So they aspire to “capture” three more protons (hydrogen ions) from a water molecules. Obviously, this substance can be stable at low temperatures and in the mediums, which are not containing hydrogen. In the air at room temperature this substance, most likely, interacting with water molecules, gradually again turns into trihydroxide R(OH)3, compensating the superfluous negative charge by three hydrogen atoms. From this it follows that substance R[O3] can simultaneously be an absorber of hydrogen and generator of oxygen at atmospheric conditions and in any mediums which contains water molecules, without any prior processing like heating or high pressure. Thus, the obtained material, without any prior processing like heating or high pressure, can simultaneously be oxygen generator and hydrogen accumulator in any mediums characteristic of R[O3] to transform into stable form R(OH)3 by selective bonding of hydrogen from the hydrogen-containing environment allowing implication of Pr[O3] as the hydrogen selective absorber. Separation (by low-temperature removal) of hydrogen out of R(OH)3 lattice can again lead to restoration of its capabilities to be a simultaneous hydrogen accumulator and oxygen generator in a medium containing water molecules.展开更多
Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon...Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.展开更多
The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor ...The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor featuring a broad spectral absorption range,is successfully employed as the electron acceptor to combine with CdS for constructing a S-scheme heterojunction.The optimized photocatalyst(CdSCuO2∶1)delivers an exceptional hydrogen evolution rate of 18.89 mmol/(g·h),4.15-fold higher compared with bare CdS.X-ray photoelectron spectroscopy(XPS)and ultraviolet-visible diffuse reflection absorption spectroscopy(UV-vis DRS)confirmed the S-scheme band structure of the composites.Moreover,the surface photovoltage(SPV)and electron paramagnetic resonance(EPR)indicated that the photogenerated electrons and photogenerated holes of CdS-CuO2∶1 were respectively transferred to the conduction band(CB)of CdS with a higher reduction potential and the valence band(VB)of CuO with a higher oxidation potential under illumination,as expected for the S-scheme mechanism.Density-functional-theory calculations of the electron density difference(EDD)disclose an interfacial electric field oriented from CdS to CuO.This built-in field suppresses charge recombination and accelerates carrier migration,rationalizing the markedly enhanced PHE activity.This study offers a novel strategy for designing S-scheme heterojunctions with high light harvesting and charge utilization toward sustainable solar-tohydrogen conversion.展开更多
Molecular hydrogen(H2)demonstrates selective antioxidant and anti-inflammatory properties with therapeutic potential across musculoskeletal conditions including osteoarthritis,rheumatoid arthritis,exercise-induced mus...Molecular hydrogen(H2)demonstrates selective antioxidant and anti-inflammatory properties with therapeutic potential across musculoskeletal conditions including osteoarthritis,rheumatoid arthritis,exercise-induced muscle damage,chronic pain syndromes,tendinopathies,and muscle atrophy.This review critically evaluates preclinical and clinical evidence for H2 therapy and identifies research gaps.A comprehensive search of PubMed,EMBASE,and Cochrane Library(up to April 2025)yielded 45 eligible studies:25 preclinical and 20 clinical trials.Preclinical models consistently showed reductions in reactive oxygen species,inflammatory cytokines,and improved cell viability.Clinical trials reported symptomatic relief in osteoarthritis,decreased Disease Activity Score 28 in rheumatoid arthritis,and accelerated clearance of muscle damage markers.Delivery methods varied-hydrogen-rich water,gas inhalation,and saline infusion-hindering direct comparison.Mechanistic biomarkers were inconsistently reported,limiting understanding of target engagement.Common limitations included small sample sizes,short durations,and protocol heterogeneity.Despite these constraints,findings suggest H2 may serve as a promising adjunctive therapy via antioxidant,anti-inflammatory,and cytoprotective mechanisms.Future research should prioritize standardized delivery protocols,robust mechanistic endpoints,and longer-term randomized trials to validate clinical efficacy and optimize therapeutic strategies.展开更多
Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via lo...Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.展开更多
Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains...Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains a confusing topic.Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures(SCSs)for Zn-ion storage with double-high capacitive activity and durability.Tetrachlorobenzoquinone(H-bond acceptor)and dimethylbenzidine(H-bond donator)can interact to form organic nanosheet modules,which are sequentially assembled,orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds(N-H···O).Featured with rich surface-active heterodiatomic motifs,more exposed nanoporous channels,and successive charge migration paths,SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers(3.3Ωs-0.5).Consequently,the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics,including high energy density(166 Wh kg-1),high-rate performance(172 m Ah g^(-1)at 20 A g^(-1)),and long-lasting cycling lifespan(95.5%capacity retention after 500,000 cycles).An opposite chargecarrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage,involving high-kinetics physical Zn^(2+)/CF_(3)SO_(3)-adsorption and chemical Zn^(2+)redox with carbonyl/pyridine groups.This work gives insights into H-bond-guided interfacial superassembly design of superstructural carbons toward advanced energy storage.展开更多
Pre-chamber ignition technology can address the issue of uneven in-cylinder mixture combustion in large-bore marine engines.The impact of various pre-chamber structures on the formation of the mixture and jet flames w...Pre-chamber ignition technology can address the issue of uneven in-cylinder mixture combustion in large-bore marine engines.The impact of various pre-chamber structures on the formation of the mixture and jet flames within the pre-chamber is explored.This study performed numerical simulations on a large-bore marine ammonia/hydrogen pre-chamber engine prototype,considering pre-chamber volume,throat diameter,the distance between the hydrogen injector and the spark plug,and the hydrogen injector angle.Compared with the original engine,when the pre-chamber volume is 73.4 ml,the throat diameter is 14 mm,the distance ratio is 0.92,and the hydrogen injector angle is 80°.Moreover,the peak pressure in the pre-chamber increased by 23.1%,and that in the main chamber increased by 46.3%.The results indicate that the performance of the original engine is greatly enhanced by altering its fuel and pre-chamber structure.展开更多
Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental ...Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.展开更多
3D printing,as a versatile additive manufacturing technique,offers high design flexibility,rapid prototyping,minimal material waste,and the capability to fabricate complex,customized geometries.These attributes make i...3D printing,as a versatile additive manufacturing technique,offers high design flexibility,rapid prototyping,minimal material waste,and the capability to fabricate complex,customized geometries.These attributes make it particularly well-suited for low-temperature hydrogen electrochemical conversion devices—specifically,proton exchange membrane fuel cells,proton exchange membrane electrolyzer cells,anion exchange membrane electrolyzer cells,and alkaline electrolyzers—which demand finely structured components such as catalyst layers,gas diffusion layers,electrodes,porous transport layers,and bipolar plates.This review provides a focused and critical summary of the current progress in applying 3D printing technologies to these key components.It begins with a concise introduction to the principles and classifications of mainstream 3D printing methods relevant to the hydrogen energy sector and proceeds to analyze their specific applications and performance impacts across different device architectures.Finally,the review identifies existing technical challenges and outlines future research directions to accelerate the integration of 3D printing in nextgeneration low-temperature hydrogen energy systems.展开更多
BACKGROUND Ulcerative colitis(UC)is a chronic and debilitating inflammatory bowel disease.Cumulative evidence indicates that excess hydrogen peroxide,a potent neutrophilic chemotactic agent,produced by colonic epithel...BACKGROUND Ulcerative colitis(UC)is a chronic and debilitating inflammatory bowel disease.Cumulative evidence indicates that excess hydrogen peroxide,a potent neutrophilic chemotactic agent,produced by colonic epithelial cells has a causal role leading to infiltration of neutrophils into the colonic mucosa and subsequent development of UC.This evidence-based mechanism identifies hydrogen peroxide as a therapeutic target for reducing agents in the treatment of UC.CASE SUMMARY Presented is a 41-year-old female with a 26-year history of refractory UC.Having developed steroid dependence and never achieving complete remission on treatment by conventional and advanced therapies,she began treatment with oral R-dihydrolipoic acid(RDLA),a lipid-soluble reducing agent with intracellular site of action.Within a week,rectal bleeding ceased.She was asymptomatic for three years until a highly stressful experience,when she noticed blood in her stool.RDLA was discontinued,and she began treatment with oral sodium thiosulfate pentahydrate(STS),a reducing agent with extracellular site of action.After a week,rectal bleeding ceased,and she resumed oral RDLA and discontinued STS.To date,she remains asymptomatic with normal stool calprotectin while on RDLA.CONCLUSION STS and RDLA are reducing agents that serve as highly effective and safe therapy for the induction and maintenance of remission in UC,even in patients refractory or poorly controlled by conventional and advanced therapies.Should preliminary findings be validated by subsequent clinical trials,the use of reducing agents could potentially prevent thousands of colectomies and represent a paradigm shift in the treatment of UC.展开更多
S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB...S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.展开更多
The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular an...The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular and cellular mechanisms by which quinolinic acid contributes to Huntington's disease pathology remain unknown. In this study, we established in vitro and in vivo models of Huntington's disease by administering quinolinic acid to the PC12 neuronal cell line and the striatum of mice, respectively. We observed a decrease in the levels of hydrogen sulfide in both PC12 cells and mouse serum, which was accompanied by down-regulation of cystathionine β-synthase, an enzyme responsible for hydrogen sulfide production. However, treatment with NaHS(a hydrogen sulfide donor) increased hydrogen sulfide levels in the neurons and in mouse serum, as well as cystathionine β-synthase expression in the neurons and the mouse striatum, while also improving oxidative imbalance and mitochondrial dysfunction in PC12 cells and the mouse striatum. These beneficial effects correlated with upregulation of nuclear factor erythroid 2-related factor 2 expression. Finally, treatment with the nuclear factor erythroid 2-related factor 2inhibitor ML385 reversed the beneficial impact of exogenous hydrogen sulfide on quinolinic acid-induced oxidative stress. Taken together, our findings show that hydrogen sulfide reduces oxidative stress in Huntington's disease by activating nuclear factor erythroid 2-related factor 2,suggesting that hydrogen sulfide is a novel neuroprotective drug candidate for treating patients with Huntington's disease.展开更多
Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by ...Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.展开更多
This study investigated the microstructure and hydrogen absorption properties of a rare-earth high-entropy alloy(HEA),YGdTbDyHo.Results indicated that the YGdTbDyHo alloy had a microstructure of equiaxed grains,with t...This study investigated the microstructure and hydrogen absorption properties of a rare-earth high-entropy alloy(HEA),YGdTbDyHo.Results indicated that the YGdTbDyHo alloy had a microstructure of equiaxed grains,with the alloy elements distributed homogeneously.Upon hydrogen absorption,the phase structure of the HEA changed from a solid solution with an hexagonal-close-packed(HCP)structure to a high-entropy hydride with an faced-centered-cubic(FCC)structure without any secondary phase precipitated.The alloy demonstrated a maximum hydrogen storage capacity of 2.33 H/M(hydrogen atom/metal atom)at 723 K,with an enthalpy change(ΔH)of-141.09 kJ·mol^(-1)and an entropy change(ΔS)of-119.14 J·mol^(-1)·K^(-1).The kinetic mechanism of hydrogen absorption was hydride nucleation and growth,with an apparent activation energy(E_(a))of 20.90 kJ·mol^(-1).Without any activation,the YGdTbDyHo alloy could absorb hydrogen quickly(180 s at 923 K)with nearly no incubation period observed.The reason for the obtained value of 2.33 H/M was that the hydrogen atoms occupied both tetrahedral and octahedral interstices.These results demonstrate the potential application of HEAs as a high-capacity hydrogen storage material with a large H/M ratio,which can be used in the deuterium storage field.展开更多
A hydrogen energy storage system(HESS)is one of the many risingmodern green innovations,using excess energy to generate hydrogen and storing it for various purposes.With that,there have been many discussions about com...A hydrogen energy storage system(HESS)is one of the many risingmodern green innovations,using excess energy to generate hydrogen and storing it for various purposes.With that,there have been many discussions about commercializing HESS and improving it further.However,the design and sizing process can be overwhelming to comprehend with various sources to examine,and understanding optimal design methodologies is crucial to optimize a HESS design.With that,this review aims to collect and analyse a wide range of HESS studies to summarise recent studies.Two different collections of studies are studied,one was sourced by the main author for preliminary readings,and another was obtained via VOSViewer.The findings from the Web of Science platform were also examined for amore comprehensive understanding.Major findings include the People’sRepublic of China has been active in HESS research,as most works and active organizations originate from this country.HESS has been mainly researched to support power generation and balance load demands,with financial analysis being the common scope of analysis.MATLAB is a common tool used for HESS design,modelling,and optimization as it can handle complex calculations.Artificial neural network(ANN)has the potential to be used to model the HESS,but additional review is required as a formof future work.From a commercialization perspective,pressurized hydrogen tanks are ideal for hydrogen storage in a HESS,but other methods can be considered after additional research and development.From this review,it can be implied that modelling works will be the way forward for HESS research,but extensive collaborations and additional review are needed.Overall,this review summarized various takeaways that future research works on HESS can use.展开更多
The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
The semiconductor photocatalysis are considered as one of the most promising candidates in hydrogen energy source and environmental remediation area.In this paper,flower-shaped SnS,is successfully combined on g-C,Ns,a...The semiconductor photocatalysis are considered as one of the most promising candidates in hydrogen energy source and environmental remediation area.In this paper,flower-shaped SnS,is successfully combined on g-C,Ns,and the well matching band structure successfully constitutes a new Type-II heterojunction.As expected,the photocatalytic hydrogen production experiment showed that the quantity of hydrogen produced on 5% SnS_(2)/C_(3)N_(5)was 922.5μmol/(g.h),which is 3.6 times higher than that of pure g-C_(3)N_(5).Meanwhile,in photocatalytic degradation of methylene blue,5%SnS2/C,Ns composite material can degrade 95% of contaminants within 40 min,showing good photocatalytic degradation performance.The mechanism study indicates that SnS_(2)/C_(3)N_(5)heterojunction improves the photogenerated charge migration rate and reduces the electron-hole recombination rate,and effectively improves the photocatalytic performance of g-C_(3)N_(5).This work provides a new idea for designing C,Ns-based heterojunctions with efficient hydrogen production and degradation performance.展开更多
The regioselective carbon-hydrogen bond functionalization reaction in atom-and step-economy holds significant potential for the late-stage elaboration of complex molecules and natural products.In recent years,the hydr...The regioselective carbon-hydrogen bond functionalization reaction in atom-and step-economy holds significant potential for the late-stage elaboration of complex molecules and natural products.In recent years,the hydrogen atom transfer strategy involving radicals has garnered considerable attention from chemists due to its high chemoselectivity and regioselectivity.However,owing to the marginal differences in bond dissociation energies(BDEs)among C(sp^(3))—H bonds,hydrogen atom transfer reactions mediated by alkyl radicals remain less-developed.A copper-catalyzed sulfone-induced regioselective C(sp^(3))—H bond heteroarylation reaction was reported.This strategy utilizes theα-alkyl radical of sulfone as an intramolecular hydrogen abstraction reagent,enabling the regioselective formation of carbon-nitrogen bonds under copper catalysis.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.51301008 and 51171003)the Beijing Natural Science Foundation,China(Grant No.1112005)
文摘In this paper, we study the effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La（1-x）PrxFe11.4Si1.6Hy hydrides. The powder x-ray diffraction patterns of the La1-xPrxFe11.4Si1.6 and its hydrides show that each of the alloys is crystallized into the single phase of cubic Na Zn13-type structure. There are hydrogen-absorbing plateaus under 0.4938 MPa and 0.4882 MPa in the absorbing curves for the La0.8Pr0.2Fe11.4Si1.6 and La0.6Pr0.4Fe11.4Si1.6 compounds. The releasing processes lag behind the absorbing process, which is obviously different from the coincidence between absorbing and releasing curves of the La Fe11.4Si1.6 compound. The remnant hydrogen content for La0.6Pr0.4Fe11.4Si1.6 is significantly more than that for La0.8Pr0.2Fe11.4Si1.6 after hydrogen desorption, indicating that more substitutions of Pr for La are beneficial to retaining more hydrogen atoms in the alloys. The values of maximum magnetic entropy change are 14.91 J/kg·K and 17.995 J/kg·K for La0.8Pr0.2Fe11.4Si1.6H0.13 and La0.6Pr0.4Fe11.4Si1.6H0.87,respectively.
基金supported by the National Natural Science Foundation of China(No.21878330)Key Research and Development Program of Ministry of Science and Technology of China(No.2019YFC1907602)Scientific Research and Technology Development Program of China National Petroleum Corporation(2020B-2116).
文摘NizP supported catalysts exhibit high catalytic activities in hydrogenation reaction,of which the particle sizes of Ni_(2)P active phases are the key influential factor.This research focus on the effect of chelators on the size of Ni_(2)P particles over wrinkle silica nanoparticles(WSNs)by introducing chelating agents EDTA and NTA during impregnation process.The characterization results show that chelators modified cata-lysts possess smaller size of Ni_(2)P particles than the unmodified Ni_(2)P catalysts.Among all the synthesized catalysts,the EDTA modified Ni_(2)PE(1.5)/WSNs catalyst possesses smallest average particle size of Ni_(2)P,only 2.6 nm.Moreover,the Ni_(2)P catalysts with the assistance of EDTA exhibits better catalytic activity than that of NTA under high reaction temperature,which can be ascribed to the strong bonding between EDTA and Ni.And the EDTA modified Ni_(2)PE(1.5)/WSNs catalyst shows highest hydrogenation ability,almost reaching 100%decalin selectivity.
文摘The phenomenon of hydrogen thermoemission out of a crystal lattice of powder rare-earth metals trihydrooxides R(OH)3 (R is La, Pr, Nd) was found. The hydrogen thermoemission out of a crystal lattice is partial or full removal of hydrogen out of the crystal lattice of powder hydrogen-containing crystal without change of symmetry of such crystal at continuous evacuation of high vacuum at evacuation temperature of Тev. which is lower than recrystallization Тrecrys. or disintegration (Tdisinteg.) temperature of this crystal: Тev. Тrecrys. Tdisineg.. By neutron diffraction it is found that low- temperature (Тevacuation = 400 - 420 K ) removal of hydrogen (by hydrogen thermoemission) out of a crystal lattice of trihydrooxide R(OH)3 under continuous high vacuum evacuating makes possible to obtain metastable “trioxide” R[O]3. Existence of such substance contradicts to the valence law (oxygen is bivalent and Pr is trivalent in hydroxides). Such “trioxide” has a superfluous negative charge: R3+O6-. So they aspire to “capture” three more protons (hydrogen ions) from a water molecules. Obviously, this substance can be stable at low temperatures and in the mediums, which are not containing hydrogen. In the air at room temperature this substance, most likely, interacting with water molecules, gradually again turns into trihydroxide R(OH)3, compensating the superfluous negative charge by three hydrogen atoms. From this it follows that substance R[O3] can simultaneously be an absorber of hydrogen and generator of oxygen at atmospheric conditions and in any mediums which contains water molecules, without any prior processing like heating or high pressure. Thus, the obtained material, without any prior processing like heating or high pressure, can simultaneously be oxygen generator and hydrogen accumulator in any mediums characteristic of R[O3] to transform into stable form R(OH)3 by selective bonding of hydrogen from the hydrogen-containing environment allowing implication of Pr[O3] as the hydrogen selective absorber. Separation (by low-temperature removal) of hydrogen out of R(OH)3 lattice can again lead to restoration of its capabilities to be a simultaneous hydrogen accumulator and oxygen generator in a medium containing water molecules.
基金Supported by the National Key Research and Development Program of China(2023YFB4104500,2023YFB4104502)the National Natural Science Foundation of China(22138013)the Taishan Scholar Project(ts201712020).
文摘Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.
文摘The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor featuring a broad spectral absorption range,is successfully employed as the electron acceptor to combine with CdS for constructing a S-scheme heterojunction.The optimized photocatalyst(CdSCuO2∶1)delivers an exceptional hydrogen evolution rate of 18.89 mmol/(g·h),4.15-fold higher compared with bare CdS.X-ray photoelectron spectroscopy(XPS)and ultraviolet-visible diffuse reflection absorption spectroscopy(UV-vis DRS)confirmed the S-scheme band structure of the composites.Moreover,the surface photovoltage(SPV)and electron paramagnetic resonance(EPR)indicated that the photogenerated electrons and photogenerated holes of CdS-CuO2∶1 were respectively transferred to the conduction band(CB)of CdS with a higher reduction potential and the valence band(VB)of CuO with a higher oxidation potential under illumination,as expected for the S-scheme mechanism.Density-functional-theory calculations of the electron density difference(EDD)disclose an interfacial electric field oriented from CdS to CuO.This built-in field suppresses charge recombination and accelerates carrier migration,rationalizing the markedly enhanced PHE activity.This study offers a novel strategy for designing S-scheme heterojunctions with high light harvesting and charge utilization toward sustainable solar-tohydrogen conversion.
文摘Molecular hydrogen(H2)demonstrates selective antioxidant and anti-inflammatory properties with therapeutic potential across musculoskeletal conditions including osteoarthritis,rheumatoid arthritis,exercise-induced muscle damage,chronic pain syndromes,tendinopathies,and muscle atrophy.This review critically evaluates preclinical and clinical evidence for H2 therapy and identifies research gaps.A comprehensive search of PubMed,EMBASE,and Cochrane Library(up to April 2025)yielded 45 eligible studies:25 preclinical and 20 clinical trials.Preclinical models consistently showed reductions in reactive oxygen species,inflammatory cytokines,and improved cell viability.Clinical trials reported symptomatic relief in osteoarthritis,decreased Disease Activity Score 28 in rheumatoid arthritis,and accelerated clearance of muscle damage markers.Delivery methods varied-hydrogen-rich water,gas inhalation,and saline infusion-hindering direct comparison.Mechanistic biomarkers were inconsistently reported,limiting understanding of target engagement.Common limitations included small sample sizes,short durations,and protocol heterogeneity.Despite these constraints,findings suggest H2 may serve as a promising adjunctive therapy via antioxidant,anti-inflammatory,and cytoprotective mechanisms.Future research should prioritize standardized delivery protocols,robust mechanistic endpoints,and longer-term randomized trials to validate clinical efficacy and optimize therapeutic strategies.
基金the National Nature Science Foundation of China for Excellent Young Scientists Fund(32222058)Fundamental Research Foundation of CAF(CAFYBB2022QB001).
文摘Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.
基金financially supported by the National Natural Science Foundation of China(Nos.22272118,22172111,and 22309134)the Science and Technology Commission of Shanghai Municipality,China(Nos.22ZR1464100,20ZR1460300,and 19DZ2271500)+2 种基金the China Postdoctoral Science Foundation(2022M712402),the Shanghai Rising-Star Program(23YF1449200)the Zhejiang Provincial Science and Technology Project(2022C01182)the Fundamental Research Funds for the Central Universities(2023-3-YB-07)。
文摘Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains a confusing topic.Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures(SCSs)for Zn-ion storage with double-high capacitive activity and durability.Tetrachlorobenzoquinone(H-bond acceptor)and dimethylbenzidine(H-bond donator)can interact to form organic nanosheet modules,which are sequentially assembled,orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds(N-H···O).Featured with rich surface-active heterodiatomic motifs,more exposed nanoporous channels,and successive charge migration paths,SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers(3.3Ωs-0.5).Consequently,the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics,including high energy density(166 Wh kg-1),high-rate performance(172 m Ah g^(-1)at 20 A g^(-1)),and long-lasting cycling lifespan(95.5%capacity retention after 500,000 cycles).An opposite chargecarrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage,involving high-kinetics physical Zn^(2+)/CF_(3)SO_(3)-adsorption and chemical Zn^(2+)redox with carbonyl/pyridine groups.This work gives insights into H-bond-guided interfacial superassembly design of superstructural carbons toward advanced energy storage.
基金Supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions under Grant No.014000319/2018-00391.
文摘Pre-chamber ignition technology can address the issue of uneven in-cylinder mixture combustion in large-bore marine engines.The impact of various pre-chamber structures on the formation of the mixture and jet flames within the pre-chamber is explored.This study performed numerical simulations on a large-bore marine ammonia/hydrogen pre-chamber engine prototype,considering pre-chamber volume,throat diameter,the distance between the hydrogen injector and the spark plug,and the hydrogen injector angle.Compared with the original engine,when the pre-chamber volume is 73.4 ml,the throat diameter is 14 mm,the distance ratio is 0.92,and the hydrogen injector angle is 80°.Moreover,the peak pressure in the pre-chamber increased by 23.1%,and that in the main chamber increased by 46.3%.The results indicate that the performance of the original engine is greatly enhanced by altering its fuel and pre-chamber structure.
基金supported by the National Natural Science Foundation of China(52002297)National Key R&D Program of China(2022VFB2404800)+1 种基金Wuhan Yellow Crane Talents Program,China Postdoctoral Science Foundation(No.2024M752495)the Postdoctoral Fellowship Program of CPSF(No.GZB20230552).
文摘Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.
基金the support from the National Natural Science Foundation of China(Nos.22208376,UA22A20429)the Qingdao New Energy Shandong Laboratory Open Project(QNESL OP 202303)+3 种基金Shandong Provincial Natural Science Foundation(Nos.ZR2024QB175,ZR2023LFG005)Fundamental Research Funds for the Central Universities(No.25CX07002A)National Natural Science Foundation of China(Z202401390008)The Hunan Provincial Natural Science Foundation(2025JJ60301)。
文摘3D printing,as a versatile additive manufacturing technique,offers high design flexibility,rapid prototyping,minimal material waste,and the capability to fabricate complex,customized geometries.These attributes make it particularly well-suited for low-temperature hydrogen electrochemical conversion devices—specifically,proton exchange membrane fuel cells,proton exchange membrane electrolyzer cells,anion exchange membrane electrolyzer cells,and alkaline electrolyzers—which demand finely structured components such as catalyst layers,gas diffusion layers,electrodes,porous transport layers,and bipolar plates.This review provides a focused and critical summary of the current progress in applying 3D printing technologies to these key components.It begins with a concise introduction to the principles and classifications of mainstream 3D printing methods relevant to the hydrogen energy sector and proceeds to analyze their specific applications and performance impacts across different device architectures.Finally,the review identifies existing technical challenges and outlines future research directions to accelerate the integration of 3D printing in nextgeneration low-temperature hydrogen energy systems.
文摘BACKGROUND Ulcerative colitis(UC)is a chronic and debilitating inflammatory bowel disease.Cumulative evidence indicates that excess hydrogen peroxide,a potent neutrophilic chemotactic agent,produced by colonic epithelial cells has a causal role leading to infiltration of neutrophils into the colonic mucosa and subsequent development of UC.This evidence-based mechanism identifies hydrogen peroxide as a therapeutic target for reducing agents in the treatment of UC.CASE SUMMARY Presented is a 41-year-old female with a 26-year history of refractory UC.Having developed steroid dependence and never achieving complete remission on treatment by conventional and advanced therapies,she began treatment with oral R-dihydrolipoic acid(RDLA),a lipid-soluble reducing agent with intracellular site of action.Within a week,rectal bleeding ceased.She was asymptomatic for three years until a highly stressful experience,when she noticed blood in her stool.RDLA was discontinued,and she began treatment with oral sodium thiosulfate pentahydrate(STS),a reducing agent with extracellular site of action.After a week,rectal bleeding ceased,and she resumed oral RDLA and discontinued STS.To date,she remains asymptomatic with normal stool calprotectin while on RDLA.CONCLUSION STS and RDLA are reducing agents that serve as highly effective and safe therapy for the induction and maintenance of remission in UC,even in patients refractory or poorly controlled by conventional and advanced therapies.Should preliminary findings be validated by subsequent clinical trials,the use of reducing agents could potentially prevent thousands of colectomies and represent a paradigm shift in the treatment of UC.
基金financially supported by the National Natural Science Foundation of China(Nos.51602018 and 51902018)the Natural Science Foundation of Beijing Municipality(No.2154052)+3 种基金the China Postdoctoral Science Foundation(No.2014M560044)the Fundamental Research Funds for the Central Universities(No.FRF-MP-20-22)USTB Research Center for International People-to-people Exchange in Science,Technology and Civilization(No.2022KFYB007)Education and Teaching Reform Foundation at University of Science and Technology Beijing(Nos.2023JGC027,KC2022QYW06,and KC2022TS09)。
文摘S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.
基金supported by the National Natural Science Foundation of China,Nos.82271327 (to ZW),82072535 (to ZW),81873768 (to ZW),and 82001253 (to TL)。
文摘The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular and cellular mechanisms by which quinolinic acid contributes to Huntington's disease pathology remain unknown. In this study, we established in vitro and in vivo models of Huntington's disease by administering quinolinic acid to the PC12 neuronal cell line and the striatum of mice, respectively. We observed a decrease in the levels of hydrogen sulfide in both PC12 cells and mouse serum, which was accompanied by down-regulation of cystathionine β-synthase, an enzyme responsible for hydrogen sulfide production. However, treatment with NaHS(a hydrogen sulfide donor) increased hydrogen sulfide levels in the neurons and in mouse serum, as well as cystathionine β-synthase expression in the neurons and the mouse striatum, while also improving oxidative imbalance and mitochondrial dysfunction in PC12 cells and the mouse striatum. These beneficial effects correlated with upregulation of nuclear factor erythroid 2-related factor 2 expression. Finally, treatment with the nuclear factor erythroid 2-related factor 2inhibitor ML385 reversed the beneficial impact of exogenous hydrogen sulfide on quinolinic acid-induced oxidative stress. Taken together, our findings show that hydrogen sulfide reduces oxidative stress in Huntington's disease by activating nuclear factor erythroid 2-related factor 2,suggesting that hydrogen sulfide is a novel neuroprotective drug candidate for treating patients with Huntington's disease.
基金support from the Czech Science Foundation,project EXPRO,No 19-27454Xsupport by the European Union under the REFRESH—Research Excellence For Region Sustainability and High-tech Industries project number CZ.10.03.01/00/22_003/0000048 via the Operational Programme Just Transition from the Ministry of the Environment of the Czech Republic+1 种基金Horizon Europe project EIC Pathfinder Open 2023,“GlaS-A-Fuels”(No.101130717)supported from ERDF/ESF,project TECHSCALE No.CZ.02.01.01/00/22_008/0004587).
文摘Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.
基金financially supported by the National Natural Science Foundation of China(Nos.21171018 and 51271021)the State Key Laboratory for Advanced Metals and Materials。
文摘This study investigated the microstructure and hydrogen absorption properties of a rare-earth high-entropy alloy(HEA),YGdTbDyHo.Results indicated that the YGdTbDyHo alloy had a microstructure of equiaxed grains,with the alloy elements distributed homogeneously.Upon hydrogen absorption,the phase structure of the HEA changed from a solid solution with an hexagonal-close-packed(HCP)structure to a high-entropy hydride with an faced-centered-cubic(FCC)structure without any secondary phase precipitated.The alloy demonstrated a maximum hydrogen storage capacity of 2.33 H/M(hydrogen atom/metal atom)at 723 K,with an enthalpy change(ΔH)of-141.09 kJ·mol^(-1)and an entropy change(ΔS)of-119.14 J·mol^(-1)·K^(-1).The kinetic mechanism of hydrogen absorption was hydride nucleation and growth,with an apparent activation energy(E_(a))of 20.90 kJ·mol^(-1).Without any activation,the YGdTbDyHo alloy could absorb hydrogen quickly(180 s at 923 K)with nearly no incubation period observed.The reason for the obtained value of 2.33 H/M was that the hydrogen atoms occupied both tetrahedral and octahedral interstices.These results demonstrate the potential application of HEAs as a high-capacity hydrogen storage material with a large H/M ratio,which can be used in the deuterium storage field.
文摘A hydrogen energy storage system(HESS)is one of the many risingmodern green innovations,using excess energy to generate hydrogen and storing it for various purposes.With that,there have been many discussions about commercializing HESS and improving it further.However,the design and sizing process can be overwhelming to comprehend with various sources to examine,and understanding optimal design methodologies is crucial to optimize a HESS design.With that,this review aims to collect and analyse a wide range of HESS studies to summarise recent studies.Two different collections of studies are studied,one was sourced by the main author for preliminary readings,and another was obtained via VOSViewer.The findings from the Web of Science platform were also examined for amore comprehensive understanding.Major findings include the People’sRepublic of China has been active in HESS research,as most works and active organizations originate from this country.HESS has been mainly researched to support power generation and balance load demands,with financial analysis being the common scope of analysis.MATLAB is a common tool used for HESS design,modelling,and optimization as it can handle complex calculations.Artificial neural network(ANN)has the potential to be used to model the HESS,but additional review is required as a formof future work.From a commercialization perspective,pressurized hydrogen tanks are ideal for hydrogen storage in a HESS,but other methods can be considered after additional research and development.From this review,it can be implied that modelling works will be the way forward for HESS research,but extensive collaborations and additional review are needed.Overall,this review summarized various takeaways that future research works on HESS can use.
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
基金This project was supported by the Fundamental Research Program of Shanxi Province(202303021221058)。
文摘The semiconductor photocatalysis are considered as one of the most promising candidates in hydrogen energy source and environmental remediation area.In this paper,flower-shaped SnS,is successfully combined on g-C,Ns,and the well matching band structure successfully constitutes a new Type-II heterojunction.As expected,the photocatalytic hydrogen production experiment showed that the quantity of hydrogen produced on 5% SnS_(2)/C_(3)N_(5)was 922.5μmol/(g.h),which is 3.6 times higher than that of pure g-C_(3)N_(5).Meanwhile,in photocatalytic degradation of methylene blue,5%SnS2/C,Ns composite material can degrade 95% of contaminants within 40 min,showing good photocatalytic degradation performance.The mechanism study indicates that SnS_(2)/C_(3)N_(5)heterojunction improves the photogenerated charge migration rate and reduces the electron-hole recombination rate,and effectively improves the photocatalytic performance of g-C_(3)N_(5).This work provides a new idea for designing C,Ns-based heterojunctions with efficient hydrogen production and degradation performance.
文摘The regioselective carbon-hydrogen bond functionalization reaction in atom-and step-economy holds significant potential for the late-stage elaboration of complex molecules and natural products.In recent years,the hydrogen atom transfer strategy involving radicals has garnered considerable attention from chemists due to its high chemoselectivity and regioselectivity.However,owing to the marginal differences in bond dissociation energies(BDEs)among C(sp^(3))—H bonds,hydrogen atom transfer reactions mediated by alkyl radicals remain less-developed.A copper-catalyzed sulfone-induced regioselective C(sp^(3))—H bond heteroarylation reaction was reported.This strategy utilizes theα-alkyl radical of sulfone as an intramolecular hydrogen abstraction reagent,enabling the regioselective formation of carbon-nitrogen bonds under copper catalysis.
